Chlorodiphenylphosphine → (3,4,5-Trimethoxyphenyl)diphenylphosphine

HRID 481114Notes

Reaction equation

HRID 481114 reaction equation
[CH3:1][O:2][C:3]1[CH:4]=[C:5](Br)[CH:6]=[C:7]([O:11][CH3:12])[C:8]=1[O:9][CH3:10].[Li]CCCC.[P:19](Cl)([C:26]1[CH:31]=[CH:30][CH:29]=[CH:28][CH:27]=1)[C:20]1[CH:25]=[CH:24][CH:23]=[CH:22][CH:21]=1>C1COCC1>[CH3:1][O:2][C:3]1[CH:4]=[C:5]([P:19]([C:26]2[CH:27]=[CH:28][CH:29]=[CH:30][CH:31]=2)[C:20]2[CH:25]=[CH:24][CH:23]=[CH:22][CH:21]=2)[CH:6]=[C:7]([O:11][CH3:12])[C:8]=1[O:9][CH3:10]

Participants

5

Reactant 3

HCID 66180ChlorodiphenylphosphineHCID 758855-Bromo-1,2,3-trimethoxybenzeneHCID 178418339Butyllithium

Product 1

HCID 14686581(3,4,5-Trimethoxyphenyl)diphenylphosphineYield 80%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Conditions

Temperature
-78 °C

Procedure

To a solution of 3,4,5-trimethoxybromobenzene 18 (62.3 g, 0.25 mol) in dry THF (200 ml) was added BuLi solution (169 ml, 1.6M in hexane, 0.27 mol) dropwise at −78° C. within 45 min. The resulting beige-colored suspension was stirred for an additional 1 h at −78° C. Then PPh2Cl (61 g, 0.277 mol, 49.7 ml) was added dropwise. The addition was complete within 2 h. The resulting yellow solution was allowed to warm to 0° C. within 2 h and quenched by addition of NH4Cl solution (200 ml). The organic layer was separated, washed with brine (250 ml), dried (Na2SO4), filtered, and evaporated. The solid was recrystallized from methanol to give 69.5 g(80%) of 19.

Workup

  1. additionThe addition
  2. waitwas complete within 2 h
  3. temperatureto warm to 0° C. within 2 h
  4. customquenched by addition of NH4Cl solution (200 ml)
  5. customThe organic layer was separated
  6. washwashed with brine (250 ml)
  7. dry with materialdried (Na2SO4)
  8. filtrationfiltered
  9. customevaporated
  10. customThe solid was recrystallized from methanol

Sources & evidence

ORD record
ord-ece53045730f4995b1d30de42a2c5800
Source dataset
uspto-grants-2003_11
Patent number
US06653485B2

Reaction notes

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